Continuous production method of methanol

Abstract

The present invention relates to a method for producing methanol from hydrogen and carbon monoxide, both in the gaseous state, in which hydrogen and carbon monoxide are contacted with a liquid in at least one bubble or loop or jet loop reactor, the liquid comprising at least one solvent, an alcohol and / or an amine as nucleophilic promoter, optionally an additional base, and a catalyst, the catalyst comprising a transition metal and at least one Lewis basic ligand. At least one device is provided for removing heat from the reactor. The methanol formed as product is then separated by at least one phase separation device.

Description

[Technical field]

[0001] The present invention relates to a process for producing methanol from hydrogen and carbon monoxide, both in gaseous state, in particular the present invention relates to the use of suitable reactors and separation of the process products. [Background technology]

[0002] <General> Methanol, also known as methyl alcohol, is an organic compound with the molecular formula CH3OH. Methanol is one of the most widely produced organic chemicals, with a current annual production of approximately 100 million tons. This is because methanol is an important starting material, in particular for the basic products of aldehydes, formic acid and acetic acid. Furthermore, methanol and its derivatives are used as an energy source, in particular methane is formed from it. Furthermore, methanol is necessary for the synthesis of biodiesel and the antiknock agent MTBE. Methanol can also play a role in the seasonal storage of electrical energy. For example, this is done through direct reconversion to electricity using fuel cells (direct methanol fuel cell) or indirect reconversion (H2 reformer) or combustion in appropriately adapted turbines. Finally, methanol is particularly important in the future for all decentralized variable energy generation processes that depend on weather conditions, i.e. solar and wind power, since it has a high volumetric and gravimetric energy density and it can be easily transported. Summary of the Invention [Problem to be solved by the invention]

[0003] <Explanation of the problem and basic technical implementation so far> Currently, industrial methanol production is mainly carried out by heterogeneous catalysis with the gaseous reactants carbon monoxide (CO) and hydrogen (H2) on solid catalysts, mainly on copper-zinc-aluminum oxides. The main drawback of this heterogeneous catalysis to produce methanol from synthesis gas is the high temperatures and pressures used. The conversion of carbon monoxide and hydrogen to methanol has a standard enthalpy of -90.6 kJ / mol, which means that the higher the temperature, the more the equilibrium is shifted towards the starting compounds carbon monoxide and hydrogen. Since heterogeneous catalysts require high activation energy and thus high temperatures, this reduces the proportion of products in the reaction equilibrium. Hence the need for high pressures to shift the equilibrium towards the products. Despite these measures, typical yields per operating cycle are only about 6-15% by weight, and unreacted CO and H2 have to be recycled at great expense. Compression of the reactants and recompression of unconsumed gases result in high energy requirements for this type of production process, which leads to a high OPEX share in the price of methanol production. In addition to the high exothermicity of the reaction itself, the high temperatures required for this type of conversion necessitate intensive cooling of the reactor, especially the catalyst. Due to the nature of this approach, which uses gaseous reactants and solid catalysts, considerable heat is released in the catalyst, whose optimal performance is only ensured at low temperatures.

[0004] The industrial production methods so far are linked to the fundamental properties of the copper-zinc-aluminium-oxide catalyst, to which the plant components and the efficient coupling of material and energy flows are also linked. However, the economic efficiency of industrial processes is always strongly influenced by two factors: the thermodynamics of the equilibrium (CO+2H2⇔CH3OH) based on reactants and products, and the activation barrier based on the catalytic approach. The so-called low-pressure process using heterogeneous catalysts can now be realized on a large scale with equally good yields, but it still uses temperatures above 200 °C and pressures of 50-100 bar. This high load on the plant components also leads to high investment costs and increases the share of CAPEX in the price of methanol production. [Means for solving the problem]

[0005] <Principle of the invention> The fundamental advantage underlying the process according to the invention is therefore that the novel catalytic process can be carried out at significantly lower temperatures, for example 150° C., and at considerably lower pressures, for example 50 bar.

[0006] The industrial process for producing methanol described herein represents a particularly economical and environmentally friendly conversion of CO and H2 to methanol, based on a novel catalytic approach with specific technical means.

[0007] A first feature of the specific technical implementation is to carry out a novel catalytic approach in a substantially gas-liquid system, which differs from previously known methods in that the reaction is mainly carried out in the liquid phase. Preferably, the catalysis is carried out as homogeneous catalysis, with the catalyst dissolved in a solvent, or an immobilized catalyst is used, and according to the novel approach, synthesis gas is converted to methanol.

[0008] The advantage of a liquid phase containing a homogeneous or immobilized catalyst is that it can directly absorb and dissipate the released heat and, unlike conventional processes, so-called hot spots do not occur, where a local temperature increase irreversibly changes the catalyst and thus renders it ineffective and / or where higher local temperatures lead to undesirable side reactions and thus to a loss of reactants without an increase in products. By using a liquid phase, the reactants H2 and CO in the gaseous state must be introduced as intensively as possible. Most industrial gas-liquid reactors are based on stirred tank or bubble column reactors with gas introduction (directly into the liquid or via an agitator).

[0009] Bubble column reactors are the least expensive form of gas-liquid reactor, which is why they are most frequently used. In addition to these typical gas-liquid reactors, there are also loop reactors for niche applications. Typical loop reactors include jet zone loop reactors, impinging jet reactors, loop venturi reactors (bus loop reactors), jet loop reactors, and jet nozzle circulation reactors (jet loop reactors). They are used in particular in the form of jet loops (jet loop reactors) in hydroformylation (homogeneous catalysis, CO + H2 + olefin → aldehyde) and biocatalytic oxidation (enzymes, substrate + O2 → oxidation products). This type of reactor has been used so far when the reaction rate is very fast, for example in hydroformylation and enzyme catalysis. Therefore, the usual gas supply to the liquid in the bubble column reactor has a limiting effect, and the reaction rate is therefore determined by the material transfer rate. Conversely, bubble column reactors are usually used when the reaction rate is slow.

[0010] The second feature is to carry out gas-liquid reactions, especially in loop reactors, but this type of reactor is not obvious at first, since the reactions on which the invention is based using previously known catalysts do not have as fast reaction rates as hydroformylation or enzymatic catalysis. However, the methanol synthesis described here is characterized in that there is no metered addition of any additional substrates (other than H2 and CO). This has the major drawback that the reaction solution is not continuously cooled by the exothermic reaction, as is the case when other components are added. The strong exothermic reaction of the methanol synthesis therefore leads to strong heating over the course of the reaction. However, catalysts, especially homogeneous catalysts, have a certain temperature range in which they catalyze the desired reaction with high selectivity. Therefore, the methanol synthesis requires intensive cooling.

[0011] The use of a loop reactor results in better mixing of gas and liquid and distribution of heat compared to other gas-liquid reactors. Heat can be removed by internal or external heat exchangers. Internal heat exchangers are directly immersed in the reaction solution (e.g. cooling coils, U-tubes, heat exchanger plates) or the reactor walls transfer the heat to the heat exchanger. If the reaction solution is circulated in a circuit, the heat can also be dissipated via a heat exchanger in this external circuit. The catalytic systems described so far are not fast enough for loop reactors, but the lack of continuous metered addition of co-substrates (except CO and H2) adds an important aspect of heat removal that makes this type of reactor particularly promising for industrial implementation.

[0012] A third feature for a particularly economical implementation of this methanol synthesis is the use of one or more reactors and one or more external heat exchangers, so that depending on the size of the production plant, the optimal combination of the individual components can be selected.

[0013] The fourth feature deals with the most economical separation of the produced methanol. This can be done in several successive steps, based on the simple principle of phase separation. For example, gas-liquid systems can be used, as well as gas-liquid-liquid subgroups, which are characterized by the presence of several liquid phases, for example one phase rich in catalyst and the other rich in product. By separating or continuously removing the product-rich phase, the total flow rate during separation of the methanol is reduced. Methanol is then removed from the product-rich phase. This can be done by using methanol-selective membranes (for example nanofiltration) or by simple (flash evaporation) or multi-stage (column) distillation.

[0014] Preferably, the method is implemented using some of the features of both independent claims 1 and 6.

[0015] In this method, the gaseous reactants hydrogen (H2) and carbon monoxide (CO) are converted to methanol. The reaction takes place in a liquid, which contains at least one solvent, an alcohol and / or amine as a nucleophilic promoter, and a catalyst. The catalyst may be in liquid form or as a solid in a liquid. The catalyst itself contains at least one Lewis basic ligand (e.g., N / NH, O / OH, S / SH, C / CH, Si / Si-H, B / BH) and a transition metal. It is a metal catalyst with the basic structure M-LB, where M is a metal ion and LB is at least one Lewis basic center. In its simplest form, the catalyst is M, as shown in the following structural formula (1): x N y (x=1-4, y=1-2).

[0016] [ka]

[0017] Simple examples are manganese nitride or iron nitride. Besides artificial manganese nitrides, natural minerals such as iron nitrides like siderazote (Fe3N) and roardite (Fe4N) are also known.

[0018] Further well suited are organometallic complexes as shown in formula (2), where M is a metal ion and LB is at least one Lewis base centre. In this variant, LB comprises at least one atom selected from the group comprising N, P, O, S or C.

[0019] [ka]

[0020] The transition metal is an ion selected from the group consisting of manganese, rhenium, iron, ruthenium, chromium, molybdenum, tungsten, cobalt, rhodium, iridium, nickel, copper, palladium, and platinum, with manganese, iron, ruthenium, and molybdenum having particularly good properties. In particular, the use of manganese, ruthenium, or molybdenum as the central ion shows a high conversion rate (TON).

[0021] Exemplary homogeneous catalysts include:

[0022] [ka]

[0023] The reaction is preferably carried out in the presence of a base. It has been found that, in particular, alcoholates can be promoted by the base. Suitable bases include phosphates, sulfates, carbonates or alcoholates of lithium, sodium, potassium or calcium. For example, the use of K3PO4 or KOMe has been successful.

[0024] The reaction can be preferably carried out in a bubble column, a loop reactor or a jet loop reactor. Such reactor types are known from the continuous reaction of a gas with at least one liquid. For example, WO 2010 / 923018 describes a process for converting compounds having olefinic double bonds into aldehydes and / or alcohols using synthesis gas.

[0025] A loop reactor consists of a tubular reactor and a material recirculation system. This makes it possible to achieve a reaction control with intermediate properties between a tubular reactor and an ideal mixed stirred tank reactor. In its basic function, a gas mixture flows into the reactor, for example from above or below, so that a column of bubbles is formed in the inner tube of the loop reactor. In addition to this actual tubular reactor, there is a material recirculation system so that the reaction volume and the residence time in the bubble reactor can be individually adjusted based on the proportion of the recycled material flow. It is therefore important that in the loop reactor there is a spatial separation between the upflow direction and the downflow direction.

[0026] Thus, a loop reactor is a special bubble column reactor in which the rising gas-laden liquid undergoes a defined circulation due to the coaxial guide tube structure. There are several types of loop reactors. In the simplest case, the gas is introduced into the guide tube through a central nozzle at the bottom of the reactor. The gas bubbles carry the liquid upwards according to the principle of an airlift pump. Over the upper edge, the liquid flows back downwards between the reactor shell and the guide tube, degassing it. The gas dispersion can be significantly improved by the addition of a propulsion jet.

[0027] There are two basic types of loop reactors, namely the external loop, where the spatial separation is clearly visible. The upflow column and the downflow column are arranged side by side as cylinders and are connected by tubes at the top and bottom. A loop reactor with an internal loop has a smaller cylinder in the center of a cylinder with a larger diameter. The connection between the two cylinders is made possible by making the ends of the smaller cylinder, which acts as a bubble reactor, slightly shorter than the surrounding cylinder. This design is used especially for larger dimensions, as it is space-saving.

[0028] The so-called jet loop reactor or jet nozzle reactor is characterized by a homogeneous distribution of gas and liquid, in which the liquid is fed in a jet stream to the bottom of the reactor so that it can capture the gas and split the gas stream.

[0029] In an impinging jet reactor, at least two separate circulation streams are generated by multiple nozzles and directed towards each other. This configuration provides a high specific power input in the impingement zone with a large mass exchange capacity. The disadvantage is that the structure is more complicated.

[0030] So-called downflow loop reactors are characterised by very long gas residence times and therefore can have a low overall height.

[0031] Loop reactors are used in many technical gas-liquid reactions. However, the focus here is on the reaction of a liquid reactant with a gaseous reactant. In this case, however, a liquid reaction environment is provided by a solvent, in which there is also a reaction product, which is also liquid, and the two reactants hydrogen and carbon monoxide are present in gaseous form. Therefore, it is not common to use loop reactors for the continuous reaction of gaseous reactants.

[0032] Furthermore, in the present application, since the reaction is highly exothermic, it is preferred that such a reactor has at least one device for heat dissipation.

[0033] This allows methanol to be produced at much lower pressures, thus significantly lowering CAPEX and OPEX costs.

[0034] Furthermore, it has proven to be advantageous to use at least two loop or jet loop reactors connected in parallel and / or in series, since in the case of a parallel connection the individual plant components can be dimensioned smaller, whereas in the case of a series connection there is the advantage that the respective degree of conversion can be controlled by the corresponding catalyst concentration, thus avoiding local temperature stresses due to strongly exothermic reactions.

[0035] With regard to the at least one heat dissipation device, in order to achieve the most uniform possible temperature control inside the reactor, it has proven advantageous to provide the heat dissipation device directly inside the reactor or on the outer shell of the reactor. However, in principle, it is also conceivable to design this device in such a way that the product stream discharged from the reactor is cooled. This simplifies the design.

[0036] It is likewise conceivable to incorporate such a heat dissipation device into the above-mentioned circulation of at least one reactor, i.e. into the recirculation of the liquid, so as to cool it again before it is again brought into contact with the reactants hydrogen and oxygen. Depending on the design of the loop reactor, this heat dissipation device is located inside or outside the reactor shell.

[0037] Furthermore, if the reactors are arranged as a jet loop bundle reactor, this is advantageous as it facilitates cooling between the individual reactors, thus allowing parallel reaction control in individual bubble columns within one apparatus. This also leads to a more uniform temperature profile.

[0038] Alternatively or additionally, the present invention also provides a method for producing methanol from gaseous hydrogen and gaseous carbon monoxide, in which hydrogen and carbon monoxide are contacted with a liquid in at least one reactor. The liquid comprises at least one solvent, an alcohol or amine as a nucleophilic promoter, and a catalyst. The catalyst comprises a transition metal and at least one Lewis basic ligand. After the reaction has taken place, the formed methanol is in a liquid phase, which is transferred after the reaction to a vessel in which a liquid phase and a gas phase are formed. The formation of this phase can optionally be supported by a pressure reduction of 5% to 90%, preferably 10% to 60%, particularly preferably 20% to 50%, or by a reduction to an absolute pressure of 1 to 20 bar, preferably 5 to 10 bar. Optionally, as a complement or alternative to the reduction in pressure, the temperature can be reduced by cooling by at least 5%, preferably at least 20%, particularly preferably at least 50%.

[0039] The resulting product-rich phase contains the desired reaction product methanol in an amount of at least 55% by weight, preferably at least 70% by weight, particularly preferably at least 90% by weight, based on the total liquid phase discharged from the reactor, while the solvent is present in the liquid phase in an amount of at least 55% by weight, preferably at least 70% by weight, particularly preferably at least 90% by weight, which makes the separation of the product and the solvent very easy.

[0040] It has proved to be particularly advantageous to recycle the liquid phase to at least one of the at least one reactor, so that on the one hand the liquid containing all components, in particular the catalyst, is practically completely recirculated, and on the other hand the methanol contained therein can be recirculated again and separated correspondingly again, so that no product losses occur.

[0041] It has further been found to be advantageous if an apparatus is connected downstream of the reactor and arranged so that the liquid phase removed from the reactor first passes through this apparatus before entering the vessel. Using this apparatus, the unreacted hydrogen and / or carbon monoxide can be separated from the liquid phase by simple phase separation. This can be facilitated by a slight reduction in pressure of the system, in particular a pressure reduction of 1-5 bar, and / or a slight reduction in temperature, for example 10-25°C, preferably 25-50°C. This allows phase separation and at the same time allows recycling to the system.

[0042] Furthermore, it has been found to be advantageous to return the separated hydrogen and / or separated carbon monoxide from the device to at least one of the at least one reactor, in this way reactant losses can be avoided and the overall efficiency of the process can be increased.

[0043] Regardless of the choice of reactor and type of purification, it has been found to be advantageous if the alcohol and / or amine as promoter in the liquid is from the group comprising methanol, glycol, pyrrole, indole, aniline and derivatives of one of these compounds.

[0044] Additionally or alternatively, it has also proven to be advantageous if the alcohol and / or amine as promoter has a linear, branched or cyclic structure. All embodiments result in particularly high conversions.

[0045] Furthermore, it has been found to be advantageous if the catalyst itself is only an indirect component of the liquid, i.e. if it is not present in liquid form but is immobilized, i.e. bound to the surface of a solid, which, for example, facilitates catalyst exchange. This solid may, for example, be a sparingly soluble oxide, silicate or polymer.

[0046] Conversely, homogeneous catalysis has the advantage that the reaction becomes virtually completely independent of mass transfer phenomena.

[0047] Furthermore, in the case of product separation by evaporation of methanol, it has been found to be preferable if at least one of the solvents is an aliphatic solvent having a boiling point higher than that of methanol, since this allows separation of the solvent residues in the resulting methanol based on simple distillation.

[0048] In the case of product separation by membrane technology, nanofiltration is particularly suitable. In this case, care must be taken that all components other than methanol used are significantly different in molar mass from methanol. Catalysts, promoters, solvents and, if necessary, bases should be significantly larger and broader than methanol.

[0049] In a further preferred embodiment, the reactor temperature is 20-180°C, preferably 50-170°C, particularly preferably 80-150°C, because at these reaction temperatures a good conversion rate can be achieved without damaging the catalyst. Pressures of 1-100 bar, preferably 5-80 bar, particularly preferably 10-50 bar, have been found to be advantageous. This allows a significant reduction in the overall load on the equipment system in any combination of the aforementioned temperature and pressure ranges, compared to conventional methanol synthesis using heterogeneous catalysts.

[0050] Finally, the process can be carried out continuously or semi-continuously, facilitating large scale application. In particular, when the process is carried out continuously, the liquid phase outflow from the reactor and / or the hydrogen and / or carbon monoxide inflow to the reactor can be used to control the process in an open or closed loop manner.

[0051] Further advantages and possible embodiments of the invention are apparent from the drawings and the description thereof, each feature being considered as disclosed both individually and in any combination. [Brief description of the drawings]

[0052] [Figure 1] FIG. 1 shows one basic design of the reactor. [Diagram 2] FIG. 2 shows the parallel connection of reactors. [Diagram 3] FIG. 3 shows another basic design of the reactor. [Figure 4] FIG. 4 shows one basic design of the reactor combined with single stage processing. [Diagram 5] FIG. 5 shows one basic design of a reactor combined with a two-stage process. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0053] 1 shows the basic design using a loop reactor. The heat exchange medium is introduced into the reactor 110 via line 131. The heat exchange medium is removed again via line 132.

[0054] The reactor contains a liquid in which a solvent, an alcohol and / or an amine, at least one nucleophilic promoter, and a catalyst are present, and a gas is injected into the reactor 110 via line 121. The gas is a so-called synthesis gas mixture consisting of hydrogen and carbon monoxide.

[0055] A product stream is withdrawn from the reactor 110 via line 122 by pump 123. Part of this stream is sent to a processing unit via line 126, while the other part is cooled by passing through a heat exchanger 125 before being returned to the reactor 110 via line 124. Line 124 can also be equipped with a device for product separation. This can be, for example, a nanofiltration system, allowing methanol to be continuously removed from the system. Optionally, upstream of the product separation device, a gas separation section for unused carbon monoxide and hydrogen can be provided, allowing gases not converted during methanol separation to escape.

[0056] 2 shows an example of a parallel connection of three loop reactors 210a, 210b and 210c. Here again, the heat exchange medium is fed via line 231, respectively. The individual feed lines are designated a, b and c, corresponding to the corresponding reactor. Similarly, the heat exchange medium is discharged again via line 232, which contains individual discharge lines 232a, 232b and 232c.

[0057] The required reactant gases, hydrogen and carbon monoxide, are introduced to reactors 210a, 210b, and 210c via line 221, which includes inlet lines 221a, 221b, and 221c. Product streams are removed from the respective reactors 210a, 210b, and 210c via lines 222a, 222b, 222c, and line 222, by pump 223. A portion of this stream is fed via line 226 to a processing unit, not shown. The remaining portion of this stream is cooled in heat exchanger 225 and returned to the reactors via line 224, which includes associated lines 224a, 224b, and 224c.

[0058] Also, a device for product separation can be installed in line 324. This can be, for example, a nanofiltration system that allows methanol to be continuously removed from the system. Optionally, a gas separation section for unused carbon monoxide and hydrogen can be installed upstream of the product separation device, allowing unconverted gases to escape during methanol separation.

[0059] 3 shows an example of the separation and withdrawal of recycle and discharge streams. For this purpose, the gaseous reactant is fed via line 321 and the part withdrawn from the circuit is discharged via line 326. The remaining part is pumped via line 322 by pump 323 and recycled via heat exchanger 325 to the associated line 324. The heat exchange medium enters the reactor 310 via line 331 and is withdrawn again via line 332.

[0060] Figure 4 shows some of the possible processes, in combination with a loop reactor, but it is emphasized that this type of process can also be conceived in any other type of reactor, similar to the one shown in Figure 5.

[0061] The heat exchange medium is introduced via line 421 and removed again via line 432. Hydrogen and carbon monoxide are introduced in gaseous state via line 421 to the liquid-filled reactor 410 according to the invention and are removed via line 422 by pump 423. A portion of the streams thus removed are re-fed to the reactor 410 via line 424 and associated heat exchanger 425.

[0062] The discharged partial stream 426 is fed to an apparatus 440, where it is separated into liquid and gas phases. This can be done by pure phase separation. If necessary, this is effected by reducing the system pressure, for example by 10-80%, preferably by 20-60%, preferably to an absolute value of 5-10 bar. A temperature reduction, preferably of 1-50%, may additionally or alternatively be carried out.

[0063] The gas phase, containing the main part of the methanol fraction, is removed via line 444. The liquid phase is returned to the reactor 410 via line 441 by pump 442, where mixing can be effected in the form shown by mixing the streams from lines 421 and 441 or via separate introduction into the reactor. Cooling in the circulation line 441 is possible by at least one heat exchanger (not shown).

[0064] Finally, FIG. 5 shows an even more complex processing system in which the use of a loop reactor with a heat exchange medium supply via line 531 and a heat exchange medium removal via line 532 is only optional.

[0065] Hydrogen and carbon monoxide are introduced as gaseous reactants into the reactor 510 via line 521 and withdrawn via line 522 by means of a pump 523. Partial recycle to the reactor 510 is carried out via line 524 and a heat exchanger 525 arranged in said line. The part of the stream from line 522 that is not recycled via line 524 is fed via line 526 to a device 550. In this device 550, the liquid and gas phases are separated. This can be done exclusively by phase separation. If necessary, this is effected by reducing the pressure of the system slightly, for example by 1% to 5%, preferably by a maximum of 5 bar. Additionally or alternatively, a temperature reduction, preferably of 1% to 5%, is also conceivable.

[0066] The gas phase is returned to the reactor via line 552 by pump 553. The liquid phase obtained therein is fed via line 551 to vessel 540 for further purification of the methanol contained therein, where a second phase is separated as described with respect to FIG.

[0067] From vessel 540, the liquid phase is returned directly or indirectly via line 542 through pump 543 to reactor 510. Further cooling is possible by means of a heat exchanger, not shown. The gas phase separated in vessel 540 is fed via line 541 to possible further methanol purification, which may be nanofiltration and / or distillation in a manner not shown.

[0068] <Example> The 10 L jet loop reactor has a combined heating-cooling primary circuit and a secondary circuit designed exclusively for cooling.

[0069] 2.48g of Mn(I)-PNP catalyst (CAS1919884-90-4) (structure below) [ka] , as well as 8.77 g of potassium methanolate (KOMe) as a base, which was dissolved in 500 mL of 1-octanol at 50° C. This alcohol also serves as a promoter, or alternatively, methanol can be used. A total of 5.0 L of 1-octanol is used as the solvent.

[0070] In a semi-continuous (semi-batch) operation, 104.5 NL / min of hydrogen and 49.8 NL / min of carbon monoxide were introduced at a pressure of 25 bar and an average temperature of 120° C. The main part of the reaction took place within 1 hour from about 110° C. and 25 bar. Under these experimental conditions, a catalyst turnover number (TON) of 208 was measured for the amount of catalyst used. [Explanation of symbols]

[0071] 110...Reactor 121, 122… lines 123…Pump 124…Line 125...Heat exchanger 126~128…Line 131, 132… lines 210a, 210b, 210c...Reactors 221, 122… lines 223…Pump 224…Line 225...Heat exchanger 226~228…Line 231, 232… lines 310...Reactor 321, 322… lines 323…Pump 324…Line 325…Heat exchanger 326~328…Line 410...Reactor 421, 422… lines 423…Pump 424…Line 425...Heat exchanger 426, 428… lines 431, 432… lines 440…Phase separation device 441…Line 442…Pump 443…Line 510...Reactor 521, 522… lines 523…Pump 524…Line 525...Heat exchanger 526~528…Line 531, 532… lines 540…Phase separation device 541, 542… lines 543…Pump 543…Line 550…Container 551, 552… lines 553…Pump

Claims

1. 1. A method for producing methanol from hydrogen and carbon monoxide, comprising the steps of: contacting hydrogen and carbon monoxide with a liquid in at least one bubble reactor, loop reactor or jet loop reactor; the liquid comprises at least one solvent, an alcohol and / or an amine as a nucleophilic promoter, optionally an additional base, and a catalyst; The catalyst comprises a transition metal and at least one Lewis basic ligand; at least one device for removing heat from the reactor is provided; Methanol is formed as the product. method.

2. 10. The method of claim 1 , using at least two bubble reactors and / or loop reactors and / or jet loop reactors connected in parallel and / or in series, method.

3. The method according to claim 1 or 2, The at least one device for removing heat is located inside the reactor or on the reactor shell. method.

4. The method according to any one of claims 1 to 3, said at least one device for removing heat is integrated into the circuit of said at least one reactor; method.

5. The method according to any one of claims 1 to 4, The reactor is a loop bundle reactor or a jet loop bundle reactor; method.

6. A method for producing methanol produced from hydrogen and carbon monoxide, comprising the steps of: contacting hydrogen and carbon monoxide with a liquid in at least one reactor; The liquid comprises at least one solvent, an alcohol or amine as a nucleophilic promoter, and optionally an additional base, and a catalyst; The catalyst comprises a transition metal and at least one Lewis basic ligand; The methanol formed is in the liquid phase, After the reaction, the liquid phase is transferred to a vessel to form a liquid phase and a gas phase; The methanol formed is present in the gas phase in an amount of at least 55% by weight, and trace amounts of the solvent, the catalyst, the nucleophilic promoter, and the base are present in the liquid phase. method.

7. 7. The method of claim 6, The methanol is produced according to a process having the characteristics described in any one of claims 1 to 5. method.

8. The method according to claim 6 or 7, The liquid phase is recycled from the vessel to at least one of the at least one reactor. method.

9. The method according to any one of claims 6 to 8, Separation of the unreacted hydrogen and unreacted carbon monoxide from the liquid phase is carried out in a device downstream of the reactor prior to entering the vessel. method.

10. 10. The method of claim 9, hydrogen and / or carbon monoxide are recycled from said apparatus to at least one of said at least one reactor; method.

11. The method according to any one of claims 6 to 10, As said alcohol and / or said amine as promoter, at least one compound is selected from the group comprising methanol, glycol, pyrrole, indole, aniline and a derivative of one of the compounds of this group; method.

12. The method according to any one of claims 6 to 11, The alcohol and / or the amine as a promoter are linear, branched or cyclic in structure; method.

13. The method according to any one of claims 6 to 12, The catalyst is present bound to the surface of a solid. method.

14. The method according to any one of claims 6 to 13, As the at least one solvent, an aliphatic solvent having a boiling point higher than methanol is used; method.

15. The method according to any one of claims 6 to 14, In the at least one reactor, the temperature is between 20 and 180° C. and the pressure is between 1 and 100 bar. method.

16. The method according to any one of claims 6 to 15, The process is carried out continuously or semi-continuously. method.

17. The method according to any one of claims 1 to 15, the process is carried out continuously and the liquid phase outflow from the reactor and / or the hydrogen and / or carbon monoxide inflow to the reactor are used to control the process in an open or closed loop manner; method.

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